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[ CAS No. 22112-79-4 ] {[proInfo.proName]}

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Chemical Structure| 22112-79-4
Chemical Structure| 22112-79-4
Structure of 22112-79-4 * Storage: {[proInfo.prStorage]}
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Product Details of [ 22112-79-4 ]

CAS No. :22112-79-4 MDL No. :MFCD06657911
Formula : C44H30N4O4 Boiling Point : -
Linear Structure Formula :- InChI Key :ZUELZXZJXUXJCH-UHFFFAOYSA-N
M.W : 678.73 Pubchem ID :135462976
Synonyms :

Safety of [ 22112-79-4 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 22112-79-4 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 22112-79-4 ]

[ 22112-79-4 ] Synthesis Path-Downstream   1~68

  • 6
  • [ 22112-79-4 ]
  • [ 112-82-3 ]
  • (5Z,10Z,14Z,19Z)-5,10,15,20-Tetrakis-(3-hexadecyloxy-phenyl)-porphyrin [ No CAS ]
  • 7
  • [ 109-97-7 ]
  • [ 100-83-4 ]
  • [ 22112-79-4 ]
YieldReaction ConditionsOperation in experiment
49.2% General procedure: (1) Prepare 560mol of pyrrole and 560mol of benzaldehyde into a mixed solution and set aside;(2) In a 2000L high-pressure titanium polymerization reactor 1 with a mechanical stirring and electric heating jacket and a distillation device on the top, add a solvent E consisting of 840L of propionic acid and 560L of cyclohexane,From the bottom of the polymerization reactor 1, N2 is bubbled to the oxygen concentration in the gas phase of the reactor top condenser outlet to be lower than 1%, and then the electrical heating jacket switch of the polymerization reactor 1 is started to heat the liquid in the polymerization reactor 1 to reflux. , Maintaining the pressure of the polymerization reactor 1 at 5.0atm, while adding the mixed solution prepared in step (1) from the top of the polymerization reactor 1 by dropwise addition, the molar concentration of pyrrole in the reaction solution is always kept lower than 0.1mol during the dropwise addition / L.The water produced by the reaction is removed from the system through a distillation device at the top of the polymerization reactor, and after condensing, it is delaminated by a liquid-liquid layering device 8 to circulate the upper oil phase back into the reaction system. The reflux ratio of the distillation column was continuously adjusted so that the water concentration in the polymerization reactor 1 was always lower than 0.05%. After the dropwise addition, the reaction was continued at the same time, and the reaction was stopped after 15 minutes. At the end of the reaction, the reaction temperature was 157.1 C. Then slowly cool it down. When the temperature in the polymerization reactor 1 drops to normal temperature, the reactants in the polymerization reactor 1 are filtered through the filtering and washing device 2 to obtain a filtrate and a crude TPP filter cake. The mass of the crude TPP filter cake is 54.8 kg. According to gas chromatography analysis, the amount of pyrrole remaining in the polymerization reaction system was 55.2 mol. The filtrate can be distilled into the polymerization solvent recovery tank 3 for distillation, and the solvent and unreacted pyrrole can be recovered. The recovered solvent and pyrrole are collected for recycling to the polymerization reactor 1 and continued to be used. The residue of the distillation kettle is discharged outside the system. deal with.(3) Add 54.8 kg of crude TPP filter cake obtained by centrifugal filtration to a 2000L oxidation reactor 4 with mechanical stirring and electric heating jacket, with condensation reflux at the top and gas distributor at the bottom, and simultaneously add 1400 kg of propylene into the kettle Acid, and simultaneously introducing nitrogen gas to replace the gas phase space in the oxidation reactor 4 to a tail oxygen concentration of less than 3%. Then, the switch of the electric heating jacket is started to heat the liquid in the oxidation reactor 4. When the liquid in the oxidation reactor 4 is heated to reflux, air is passed through to carry out the oxidation reaction. The oxidation reaction time is 22 minutes. During the reaction, the oxygen concentration in the tail gas is strictly controlled by adjusting the amount of the air to be passed to less than 3%. After the oxidation reaction was completed, it was left to cool slowly. When the temperature of the liquid in the oxidation reactor 4 is reduced to normal temperature, it is put into a filtering and washing device 5 for filtration to obtain a filtrate and a solid. The filtrate is dehydrated through an oxidation reaction solvent recovery tower 6 and dehydrated and recovered to obtain propionic acid, and the recovered propionic acid is collected. After that, it is ready to be used in the recycle and oxidation reactor 4 and the residue of the tower kettle is discharged out of the system. The filtrate can also be directly recycled to the oxidation reactor 4 without any treatment and continued to be used. The solid obtained by filtration was repeatedly washed with hot water and then filtered until the filtrate was colorless. Then repeatedly wash with methanol and then filter until the filtered wastewater is freecolor. The solid washed with methanol is the product TPP, and 46.0 kg of a tetraphenylporphine product is obtained after drying in a drying device 7 under vacuum at 80 C.The yield of the product TPP based on the pyrrole of the reactant was 59.3%, and the purity was 99.2%.
46.3% (1) 560 mol of pyrrole and 560 mol of benzaldehyde were mixed to prepare a mixed solution, alternate;(2) In a 2000L titanium high pressure polymerization reactor 1 with mechanically stirred and electrically heated jacket with distillation device on top, solvent E consisting of 840L propionic acid and 560L cyclohexane was added, and the concentration of oxygen in the gas phase from the bottom of the polymerization reactor 1 where N2 is bubbled into the top of the reactor condenser was less than 1%,then, the polymerization reactor 1 was started to heat the jacket switch, the liquid in the polymerization reactor 1 was heated to reflux, maintaining the polymerization reactor 1 pressure 5.0 atm, at the same time, the mixed solution prepared in step (1) was added dropwise from the top of the polymerization reactor 1 in a dropwise manner, and the molar concentration of pyrrole in the reaction liquid was maintained at less than 0.1 mol/L during the dropwise addition. The water produced by the reaction was removed from the system through the distillation device at the top of the polymerization reactor 1, condensed, and then separated by the liquid-liquid layering device 4, and the upper oil phase was recycled back to the reaction system. The reflux ratio of the distillation column was constantly adjusted so that the water concentration in the polymerization reactor 1 was always lower than 0.05%.After the addition, the reaction was continued at the same time, and the reaction was stopped after 15 minutes. At the end of the reaction, the reaction temperature was 157.1C. At this point, the polymerization reactor 1 is maintained at a pressure of 5 atm, air was passed into the oxidation reaction, oxidation reaction time was 22 minutes, during the reaction, the oxygen concentration in the exhaust gas was strictly controlled to be less than 2% by adjusting the amount of passed air. After completion of the oxidation reaction, left to cool slowly. When the temperature of the liquid in the polymerization reactor 1 drops to room temperature, it was filtered through the filter washing device 2 to obtain the filtrate and filter cake, and the filtrate was subjected to rectification and dehydration in the solvent recovery column 3 of the polymerization reaction to recover the solvent,the recovered solvent is collected to be recycled back to the system for continued use, and the residue of the tower reactor is discharged out of the system. The filtered cake was repeatedly washed with hot water and filtered until the filtrate was colorless. The filter cake was then washed repeatedly with methanol and filtered until the filtered waste water was colorless. The filter cake washed with methanol was the product TPP, after vacuum drying at 80C51.4of 98.7%. The process flow is the same as that of Embodiment 1, except that: (1) Add 630 mol of pyrrole and 600 mol of hydroxybenzaldehyde; (2) Solvent E is a mixture of 840L propionic acid and 560L cyclohexane; (3) The reaction time in the polymerization reactor is 24 minutes and the reaction pressure is 4atm. At the end of the reaction, the reaction temperature was 146.2C. The concentration of water in the polymerization reactor is controlled to be always lower than 0.04%; (4) The gas introduced into the oxidation reactor is air, the reaction time is 54 minutes, and the reaction pressure is normal pressure; According to this method, the final solid obtained after vacuum drying at 80 C to obtain product TPP49.5kg. The product TPP had a synthesis yield of 46.3% and a purity of 98.6% based on the reactant pyridine.
9% In propionic acid; for 1.5h;Reflux; A solution of 3-hydroxybenzaldehyde (8.8 g, 72 mmol) in propionic acid (300 mL) was brought to reflux. Pyrrole (5 mL, 72 mmol) was added quickly. The resulting mixture was refluxing during additional 1.5 h. After that 200 mL of propionic acid was evaporated. Cooled to room temperature residue was neutralized with saturated solution of NaHCO3. Precipitated crude porphyrin was washed with chloroform and finally chromatographed on silica gel column with dichloromethane-methanol (30:1, v/v) mixture as eluent to give 1.11 g (9%) of 1.1H NMR (400 MHz, DMSO-d6): δ(ppm): 10.00 (s, 4H, OH), 8.88(s, 8H, βH), 7.66-7.56 (m, 12H, ArH), 7.27-7.21 (m, 4H, ArH), 3.02 (s, 2H, NH); ESI MS (m/z): 680.1 [M + H]+. Tetrakis-5,10,15,20-(3-hydroxyphenyl)chlorine (2) was obtained according to [15].
With propionic acid; at 20 - 140℃; for 14h;Heating / reflux; COMPOUND 21; 5,10, 15,20-tetrakis-(3 -Hy droxy-phenyl)-porphyrin; 3-Hydroxybenzaldehyde (0.910 g, 7.45 mmol) is dissolved in propionic acid (50 mL) and heated to 14O0C. Pyrrole (0.52 mL, 7.45 mmol) is added in one portion and the mixture heated at reflux for 2h. Stirring is continued for an additional 12 h at room temperature. Propionic acid is removed in vacuo and the residue dissolved in acetone and purified by chromatography on a column (250 g) of silica which is eluted with toluene containing a continuously increasing proportion of ethyl acetate. The product is eluted with toluene: ethyl acetate (6:1 by vol.). Solvent is removed in vacuo to afford the product as a violet solid.1H-NMR: δH (300 MHz, d6-acetone): 7.18 (d, 4H, 3J= 8.25 Hz)5 7.49 (t, 4H, 3J= 8.25 Hz), 7.56-7,62 (m, 8H)5 8.81 (m, 8 H)
In propionic acid; for 14h;Heating / reflux; 3-Hydroxybenzaldehyde (0.910 g, 7.45 mmol) is dissolved in propionic acid (50 ML) and heated to 140C. Pyrrole (0.52 mL, 7.45 mmol) is added in one portion and the mixture heated at reflux for 2h. Stirring is continued for an additional 12 h at room temperature. Propionic acid is removed in vacuo and the residue dissolved in acetone and purified by chromatography on a column (250 g) of silica which is eluted with toluene containing a continuously increasing proportion of ethyl acetate. The product is eluted with toluene: ethyl acetate (6: 1 by vol. ). Solvent is removed in vacuo to afford the product as a violet solid. 1H-NMR : 5H (300 MHz, d6-acetone): 7.18 (d, 4H, 3J= 8.25 Hz), 7.49 (t, 4H, 3J= 8.25 Hz), 7.56-7. 62 (M, 8H), 8.81 (m, 8 H)
General procedure: Propionic acid (180 mL) was added to 7.30 g of itsanhydride and heated for 5 min at 140 C. Then, 5.00 g of pyrrole (distilled), and 80 mmolof p-anisaldehyde/m-hydroxybenzaldehyde/m-formylbenzoic acid were added, stirred at140 C for 1 h and the mixture cooled to rt. Then 100 mL of EtOH was added, stirred atrt for 1 h, and filtered. The obtained residue was dried in vacuo and subjected to neutralalumina-packed-CC with eluent CHCl3 to obtain the pure porphyrins, TpAP, TmHPP,and TmCPP.

  • 8
  • C44H36N4O4 [ No CAS ]
  • [ 22112-79-4 ]
  • 10
  • [ 22112-79-4 ]
  • [ 3132-64-7 ]
  • 5,10,15,20-tetrakis[3-(2,3-epoxy-1-propyloxy)phenyl]porphyrin [ No CAS ]
  • 11
  • [ 67-56-1 ]
  • [ 22112-79-4 ]
  • [ 541-59-3 ]
  • [ 19438-10-9 ]
  • 5-(3,4-benzoquinonyl)-10,15,20-tris(3-hydroxyphenyl)porphyrin [ No CAS ]
  • 12
  • [ 22112-79-4 ]
  • 5,15-bis(3,4-benzoquinonyl)-10,20-bis(3-hydroxyphenyl)porphyrin [ No CAS ]
  • 5,10-bis(3,4-benzoquinonyl)-15,20-bis(3-hydroxyphenyl)porphyrin [ No CAS ]
  • 5,10,15-tris(3,4-benzoquinonyl)-20-(3-hydroxyphenyl)porphyrin [ No CAS ]
  • 5,10,15,20-tetrakis(3,4-benzoquinonyl)porphyrin [ No CAS ]
  • 13
  • [ 22112-79-4 ]
  • [ 15537-87-8 ]
  • 5,10,15,20-tetrakis(3'-N-dodecylamidemethoxyphenyl)porphine [ No CAS ]
  • 14
  • [ 22112-79-4 ]
  • temoporfin [ No CAS ]
  • 15
  • [ 22112-79-4 ]
  • C88H58O8N8 [ No CAS ]
  • 18
  • [ 22112-79-4 ]
  • [ 1576-35-8 ]
  • 2,3-dihydro-5,10,15,20-tetra(m-hydroxyphenyl) porphyrin ("Dihydro meta-HK7") [ No CAS ]
  • temoporfin [ No CAS ]
YieldReaction ConditionsOperation in experiment
59 mg (37%) With pyridine; o-tetrachloroquinone; potassium carbonate; EXAMPLE 2 Synthesis of 2,3-dihydro-5,10,15,20-tetra(m-hydroxyphenyl) porphyrin ("Dihydro meta-HK7") The method was as described above starting with the following reagents: 5,10,15,20-tetra(m-hydroxyphenyl) porphyrin (160 mg, 0.23 mmoles), p-toluenesulphonhydrazide (90 mg, 0.48 mmoles), anhydrous potassium carbonate (303 mg), anhydrous pyridine (11.25 ml), and o-chloranil (106 mg, 0.43 mmoles). The middle cut from the crystallisation from methanol-distilled water gave 59 mg (37%) of 2,3-dihydro-5,10,15,20-tetra(m-hydroxyphenyl)porphyrin as a purple solid. Mass spectrum (FAB) (M+H)+ 681. C44 H32 N4 O4 requires M 680. Electronic spectrum λmax (MeOH) (ε) 284 (16900), 306 (15600), 415 (146000), 516 (11000) 543 (7300), 591 (4400), and 650 (22400). Rf 0.52 on Merck silica gel irrigated with MeOH:CHCl3 (1:4).
  • 19
  • [ 22112-79-4 ]
  • [ 102498-02-2 ]
  • 20
  • [ 22112-79-4 ]
  • [ 6482-24-2 ]
  • C56H54N4O8 [ No CAS ]
  • 21
  • [ 22112-79-4 ]
  • [ 540-51-2 ]
  • 5,10,15,20-tetrakis[3-(2-hydroxyethoxy)phenyl]porphyrin [ No CAS ]
  • 22
  • [ 22112-79-4 ]
  • [ 540-51-2 ]
  • C46H34N4O5 [ No CAS ]
  • C48H38N4O6 [ No CAS ]
  • C48H38N4O6 [ No CAS ]
  • C50H42N4O7 [ No CAS ]
  • 23
  • [ 22112-79-4 ]
  • [ 591751-85-8 ]
  • 24
  • C112H162N8O8 [ No CAS ]
  • [ 22112-79-4 ]
  • C44H30N4O4*C112H162N8O8 [ No CAS ]
  • 25
  • C44H30N4O4*C112H162N8O8 [ No CAS ]
  • C112H162N8O8 [ No CAS ]
  • [ 22112-79-4 ]
  • 26
  • [ 22112-79-4 ]
  • [ 1207995-76-3 ]
  • 28
  • Temoporfin [ No CAS ]
  • [ 22112-79-4 ]
  • temoporfin [ No CAS ]
  • 29
  • [ 22112-79-4 ]
  • [ 102498-02-2 ]
  • 30
  • [ 22112-79-4 ]
  • [ 2243-54-1 ]
  • C88H58N8O8 [ No CAS ]
  • 31
  • 3-iodopropyl nonadeca-O-acetylmaltohexaoside [ No CAS ]
  • [ 22112-79-4 ]
  • 5-{3-[3-(nonadeca-O-acetylmaltohexaosyloxy)propyloxy]phenyl}-10,15,20-tris(3-hydroxyphenyl)porphyrin [ No CAS ]
  • 32
  • [ 34231-78-2 ]
  • [ 22112-79-4 ]
  • 33
  • 5,10,15,20-tetrakis(3-acetoxyphenyl)-porphyrin [ No CAS ]
  • [ 22112-79-4 ]
YieldReaction ConditionsOperation in experiment
97% With hydrogenchloride; In ethanol; water; for 1h;Reflux; Porphyrin H2(m-OCOMe)TPP (0.25 g, 0.30 mmol)was combined with EtOH (0.6 mL), H2O (1.6 mL), and concentrated HCl (0.6 mL), and stirred at reflux for 1 h. After cooling to room temperature, the mixture was diluted with H2O (15 mL), and 5% NaOH was added until the green solution turned dark red and pH was 7.5. The mixture was stirred vigorously for 30 min, ethyl acetate was added, and the mixture again stirred for 30 min. The layers were separated, washed twice with water, dried over anhydrous MgSO4, filtered, and concentrated to give 0.19 g (97%) 8: Rf ¼ 0.41 (2:1 toluene:ethyl acetate); 1H NMR d e 2.99 (s, 2H), 7.24 (d, J ¼ 7.6 Hz, 4H), 7.60 (d, J ¼ 7.5 Hz, 12H), 8.88 (s, 8H), 9.89 (s, 4H); Q-TOF obsd 679.2389 (M+H)þ, calcd 678.2267 (M ¼ C44H30N4O4).
  • 34
  • [ 22112-79-4 ]
  • [ 106-96-7 ]
  • C47H32N4O4 [ No CAS ]
  • 35
  • [ 22112-79-4 ]
  • [ 112-82-3 ]
  • 5-(3-hexadecyloxyphenyl)-10,15,20-tris(3-hydroxyphenyl)porphyrine [ No CAS ]
YieldReaction ConditionsOperation in experiment
14% General procedure: A 0.262 g (0.386 mmol) of 5 was stirred in 5 mL dimethylformamide with 0.024 g (0.579 mmol) 60% NaH for 30 min at room temperature. 0.118 g (0.386 mmol) of 1-bromohexadecane was added. The reaction mixture was stirred for 24 h at 80-90ο C. The solvent was evaporated in vacuum then water (100 mL) was added and the resulting mixture was extracted three times (3 50 mL) with dichloromethane-ethyl acetate (3:2) mixture. Combined organic fraction was washed with water (3 x 100 mL), dried with anhydrous Na2SO4. Solvents were evaporated and the residue was chromatographed on silica gel with chloroform-ethylacetate (5:1, v/v). Yield: 0.056 g (16%). 1H NMR (400 MHz, DMSO-d6): δ (ppm) 9.99 (s, 3H, OH), 8.88 (m,8H, βH), 7.99 (d, 8H, J = 8.0 Hz, ArH), 7.21 (d, 8H, J = 8.0 Hz, ArH), 4.11 (t, 2H, OCH2CH2), 1.83-1.71 (m, 2H, OCH2CH2), 1.50-1.39 (m,2H, OCH2CH2CH2), 1.29-1.10 (m, 24H, CH2), 0.78 (t, 3H, CH3), 2.85(s, 2H, NH); ESI MS (m/z): 905.0 [M + H]+.
  • 36
  • [ 22112-79-4 ]
  • [ 112-67-4 ]
  • [5-(3-oxyphenyl)-10,15,20-tris(3-hydroxyphenyl)porphyrine] palmitate [ No CAS ]
YieldReaction ConditionsOperation in experiment
18% In N,N-dimethyl-formamide; at 80℃; for 48h; General procedure: 0.212 g (0.313 mmol) of 5 was stirred in 5 mL dimethylformamide with 0.082 g (0.3 mmol) of palmitoyl chloride. The reaction mixture was stirred for 48 h at 80 οC. Water (100 mL) and triethylamine (2 mL) were added and the resulting mixture was extracted four times (4 x 50 mL) with chloroform-ethyl acetate (3:2) mixture. Combined organic fraction was washed with water (5 x 50 mL), dried with anhydrous Na2SO4. Solvents were evaporated and the residue was chromatographed on silica gel with chloroform-ethyl acetate (5:1, v/v). Yield: 0.061 g (22%). 1H NMR (400 MHz, DMSO-d6): δ (ppm) 9.95 (s, 3H, OH), 8.88 (m,6H, βH), 8.70 (d, 2H, βH), 8.23 (d, 2H, J = 8.8 Hz, ArH), 8.00 (d, 6H, J = 8.4 Hz, ArH), 7.56 (d, 2H, J = 8.8 Hz, ArH), 7.20 (d, 6H, J =8.4 Hz,ArH), 2.75 (t, 2H), 1.79 (q, 2H), 1.71 (q, 2H), 1.60 (q, 2H), 1.30-1.18 (m, 20H), 0.80 (t, 3H, CH3), 2.88 (s, 2H, NH). ESI MS (m/z): 919.0 [M + H]+.
  • 37
  • [ 22112-79-4 ]
  • [ 67217-55-4 ]
  • 6-mono-(10,15,20-tris-(3-hydroxyphenyl)-5-(3-phenoxy)-21,23-H-porphyrinyl)-β-cyclodextrin [ No CAS ]
  • 38
  • [ 22112-79-4 ]
  • temoporfin [ No CAS ]
  • 39
  • [ 22112-79-4 ]
  • [ 107-08-4 ]
  • C47H36N4O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
34% General procedure: 5,10,15,20-Tetrakis(3-hydroxyphenyl)porphyrin, m-THPP (1 equiv), was placed in a 50 mL round-bottom flask with a magnetic stirrer flashed with Ar. Dry DMF (5-10 mL) and K2CO3 (2 equiv) were added and stirred at rt for 30 min. _Different alkyl halides branched and/or with different chain length (2 equiv) were then added and the reaction progress was monitored by TLC analysis. The reaction was completed within 2.5-4 h. The reaction mixture was diluted with CH2Cl2 (100-150 mL) and washed with NaHCO3 (50 mL×3), water (50 mL×3) and brine (100 mL×3). The organic layer was dried over MgSO4 and the solvent removed in vacuo. The residue was purified by column chromatography (CH2Cl2/n-hexane/MeOH, 3: 1: 0.1, v/v/v). 4.5.2 5,10,15-Tris(3-hydroxyphenyl)-20-[(propyloxy)phenyl] porphyrin (12a) 30 Using the general procedure, m-THPP (500 mg, 0.74 mmol), K2CO3 (200 mg, 1.5 mmol), and 1-iodopropane (0.14 mL, 1.5 mmol) were dissolved in DMF (10 mL) and reacted to afford 12a as a purple solid (178 mg, 0.25 mmol, 34%). Rf (CH2Cl2/n-hexane/MeOH, 3:1:0.1 v/v/v) 0.4; mp>300 C; δH (600 MHz, (CD3)2SO2) 9.90 (s, 3H, Ar-OH), 8.91 (br s, 8H, β-H), 7.78 (br s, 2H, Ar-H), 7.68 (m, 1H, Ar-H), 7.62 (m, 9H, Ar-H), 7.38 (m, 1H, Ar-H), 7.25 (m, Ar-H), 4.13 (br s, 2H, OCH2), 1.82 (m, 2H, CH2), 1.02 (t, J=7.3 Hz, 3H, CH3), -2.94 ppm (s, 2H, NH).
  • 40
  • [ 111-25-1 ]
  • [ 22112-79-4 ]
  • C50H42N4O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
30% General procedure: 5,10,15,20-Tetrakis(3-hydroxyphenyl)porphyrin, m-THPP (1 equiv), was placed in a 50 mL round-bottom flask with a magnetic stirrer flashed with Ar. Dry DMF (5-10 mL) and K2CO3 (2 equiv) were added and stirred at rt for 30 min. _Different alkyl halides branched and/or with different chain length (2 equiv) were then added and the reaction progress was monitored by TLC analysis. The reaction was completed within 2.5-4 h. The reaction mixture was diluted with CH2Cl2 (100-150 mL) and washed with NaHCO3 (50 mL×3), water (50 mL×3) and brine (100 mL×3). The organic layer was dried over MgSO4 and the solvent removed in vacuo. The residue was purified by column chromatography (CH2Cl2/n-hexane/MeOH, 3: 1: 0.1, v/v/v). 4.5.3 5,10,15-Tris(3-hydroxyphenyl)-20-[(hexyloxy)phenyl] porphyrin (12b) Using the general procedure, m-THPP (100 mg, 0.15 mmol), K2CO3 (40 mg, 0.29 mmol), and 1-bromohexane (0.04 mL, 0.29 mmol) were dissolved in DMF (5 mL) and reacted to afford 12b as a purple solid (34 mg, 0.45 mmol, 30%). Rf (CH2Cl2/n-hexane/MeOH, 3:1:0.1, v/v/v) 0.37; mp=209-212 C; δH (600 MHz, (CD3)2SO2) 9.88 (s, 3H, Ar-OH), 8.88 (m, 8H, β-H), 7.76 (br s, 2H, Ar-H), 7.67 (br s, 1H, Ar-H), 7.59 (m, 9H, Ar-H), 7.36 (d, J=7.8 Hz, 1H, Ar-H), 7.23 (d, J=7.8 Hz, 3H, Ar-H), 4.12 (br s, 2H, OCH2), 1.75 (m, 2H, CH2), 1.41 (m, 2H, CH2), 1.26 (m, 4H, CH2), 0.81 (br s, 3H, CH3), -2.96 ppm (s, 2H, NH); δC (150 MHz, (CD3)2SO2) 158.7, 157.3, 144.1, 143.9, 129.3, 128.6, 127.3, 123.3, 122.3, 121.4, 121.2, 118.3, 116.6, 115.8, 69.2, 32.5, 30.2, 26.7, 23.5, 15.3 ppm; HRMS (MALDI) m/z calcd for C50H42N4O4=762.3206 (M)+ found=762.3226; UV-vis (CH2Cl2): λmax (log ε)=418 (5.81), 514 (4.43), 550 (3.97), 591 (3.92), 646 nm (3.75).
  • 41
  • [ 765-09-3 ]
  • [ 22112-79-4 ]
  • C57H56N4O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
40% General procedure: 5,10,15,20-Tetrakis(3-hydroxyphenyl)porphyrin, m-THPP (1 equiv), was placed in a 50 mL round-bottom flask with a magnetic stirrer flashed with Ar. Dry DMF (5-10 mL) and K2CO3 (2 equiv) were added and stirred at rt for 30 min. _Different alkyl halides branched and/or with different chain length (2 equiv) were then added and the reaction progress was monitored by TLC analysis. The reaction was completed within 2.5-4 h. The reaction mixture was diluted with CH2Cl2 (100-150 mL) and washed with NaHCO3 (50 mL×3), water (50 mL×3) and brine (100 mL×3). The organic layer was dried over MgSO4 and the solvent removed in vacuo. The residue was purified by column chromatography (CH2Cl2/n-hexane/MeOH, 3: 1: 0.1, v/v/v). 4.5.4 5,10,15-Tris(3-hydroxyphenyl)-20-[(tridecyloxy)phenyl] porphyrin (12c) Using the general procedure, m-THPP (100 mg, 0.15 mmol), K2CO3 (40 mg, 0.29 mmol) and 1-bromotridecane (0.08 mL, 0.29 mmol) were dissolved in DMF (5 mL) and reacted to afford 12c as a purple solid (50 mg, 0.06 mmol, 40%). Rf (CH2Cl2/n-hexane/MeOH, 3:1:0.15, v/v/v) 0.41; mp=186-188 C; δH (600 MHz, (CD3)2SO2) 9.88 (s, 3H, Ar-OH), 8.89 (m, 8H, β-H), 7.77 (m, 2H, Ar-H), 7.70 (t, J=8 Hz, 1H, Ar-H), 7.61 (m, 9H, Ar-H), 7.40 (d, J=8 Hz, 1H, Ar-H), 7.25 (d, J=7.9 Hz, 3H, Ar-H), 4.17 (br s, 2H, OCH2), 1.79 (m, 2H, CH2), 1.44 (m, 2H, CH2), 1.32 (m, 2H, CH2), 1.24 (m, 4H, CH2), 1.15 (m, 16H, CH2), 0.75 (t, J=6.9 Hz, 3H, CH3), -2.96 ppm (s, 2H, NH); δC (150 MHz, (CD3)2SO2) 157.4, 156.1, 142.9, 142.7, 128.1, 127.4, 126.1, 122.1, 121.1, 120.2, 120.2, 119.9, 115.4, 114.7, 68.0, 31.5, 29.3, 29.2, 29.2, 29.2, 28.9, 28.8, 25.8, 22.3, 14.2 ppm; HRMS (MALDI) m/z calcd for C57H56N4O4=860.4302 (M)+ found=860.4276; UV-vis (CH2Cl2): λmax (log ε)=418 (5.95), 514 (4.53), 550 (4.03), 590 (4.00), 646 nm (3.82).
  • 42
  • [ 52152-71-3 ]
  • [ 22112-79-4 ]
  • C48H38N4O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
30% General procedure: 5,10,15,20-Tetrakis(3-hydroxyphenyl)porphyrin, m-THPP (1 equiv), was placed in a 50 mL round-bottom flask with a magnetic stirrer flashed with Ar. Dry DMF (5-10 mL) and K2CO3 (2 equiv) were added and stirred at rt for 30 min. _Different alkyl halides branched and/or with different chain length (2 equiv) were then added and the reaction progress was monitored by TLC analysis. The reaction was completed within 2.5-4 h. The reaction mixture was diluted with CH2Cl2 (100-150 mL) and washed with NaHCO3 (50 mL×3), water (50 mL×3) and brine (100 mL×3). The organic layer was dried over MgSO4 and the solvent removed in vacuo. The residue was purified by column chromatography (CH2Cl2/n-hexane/MeOH, 3: 1: 0.1, v/v/v). 4.5.5 5,10,15-Tris(3-hydroxyphenyl)-20-[(but-2-yl-oxy)phenyl] porphyrin (12d) Using the general procedure, m-THPP (340 mg, 0.46 mmol), K2CO3 (1 mmol), and 2-iodobutane (0.12 mL, 1 mmol) were dissolved in DMF (7 mL) and reacted to afford 12d as a purple solid (34 mg, 0.05 mmol, 30%). Rf (CH2Cl2/n-hexane/MeOH, 3:1:0.1 v/v/v) 0.48; mp=215-217 C; δH (600 MHz, (CD3)2SO2) 9.89 (s, 3H, Ar-OH), 8.89 (m, 8H, β-H), 7.76 (m, 2H, Ar-H), 7.70 (t, J=7.7 Hz, 1H, Ar-H), 7.62 (m, 9H, Ar-H), 7.39 (d, J=7.7 Hz, 1H, Ar-H), 7.24 (d, J=7.8 Hz, 3H, Ar-H), 4.63 (m, 1H, OCH), 1.79 (m, 1H, CH2), 1.70 (m, 1H, CH2), 1.38 (m, 3H, CH3), 0.99 (t, J=6.9 Hz, 3H, CH3), -2.95 ppm (s, 2H, NH); δc (150 MHz, (CD3)2SO2) 156.2, 155.7, 142.5, 142.4, 127.9, 127.8, 126.9, 125.8, 121.8, 119.9, 119.9, 119.6, 115.7, 115.1, 74.4, 28.7, 19.1, 9.5 ppm; HRMS (MALDI) m/z calcd for C48H38N4O4=734.2896 (M)+ found=734.2893; UV-vis (CH2Cl2): λmax (log ε)=418 (5.89), 514 (4.48), 549 (4.02), 589 (3.99), 646 nm (3.87).
  • 43
  • [ 22112-79-4 ]
  • [ 74-88-4 ]
  • 5,10,15-tris(3-hydroxyphenyl)-20-(3-methoxyphenyl)porphyrin [ No CAS ]
  • 5,10-bis(3-hydroxyphenyl)-15,20-bis(3-methoxyphenyl)porphyrin [ No CAS ]
  • 5-(3-hydroxyphenyl)-10,15,20-tris(3-methoxyphenyl)porphyrin [ No CAS ]
  • 44
  • [ 22112-79-4 ]
  • [ 74-88-4 ]
  • [ 29114-93-0 ]
  • 5,10,15-tris(3-hydroxyphenyl)-20-(3-methoxyphenyl)porphyrin [ No CAS ]
  • 5,10-bis(3-hydroxyphenyl)-15,20-bis(3-methoxyphenyl)porphyrin [ No CAS ]
  • 5-(3-hydroxyphenyl)-10,15,20-tris(3-methoxyphenyl)porphyrin [ No CAS ]
  • 45
  • [ 22112-79-4 ]
  • [ 74-88-4 ]
  • [ 29114-93-0 ]
  • 5,10-bis(3-hydroxyphenyl)-15,20-bis(3-methoxyphenyl)porphyrin [ No CAS ]
  • 5-(3-hydroxyphenyl)-10,15,20-tris(3-methoxyphenyl)porphyrin [ No CAS ]
  • 46
  • [ 22112-79-4 ]
  • [ 74-88-4 ]
  • [ 29114-93-0 ]
  • 47
  • [ 54245-42-0 ]
  • [ 22112-79-4 ]
  • 5,10,15-tris(3-hydroxyphenyl)-20-(3-[(11)C]methoxyphenyl)porphyrin [ No CAS ]
  • 49
  • [ 22112-79-4 ]
  • [ 5970-45-6 ]
  • [ 102498-02-2 ]
YieldReaction ConditionsOperation in experiment
89% In water; for 0.5h;Sonication; A mixture of the porphyrin (50 mg), the metal salt (1 equivalent) and 1 mL of wateror NaOH (2 M) aqueous solution were placed in a glass container (microwave reactorglass vial-10 mL) and placed into the ultrasound bath (Bandelin Sonorex RK100H) ensuringthat all the reaction solution is below the level of the water at the ultrasound bath(ca. 1 cm depth). The reaction was followed by UV-Vis at each 10 min. Once complete, thereaction was neutralized with HCl (1 M) solution. The hydrophobic porphyrins werepurified through liquid-liquid extraction using ethyl acetate, the organic phase was driedwith Na2SO4 anhydride and the solvent removed through evaporation. Water-solubleporphyrins were purified through exclusion chromatography (Sephadex G-10) usingwater as eluent, followed by water evaporation.
  • 50
  • cobalt(II) chloride hexahydrate [ No CAS ]
  • [ 22112-79-4 ]
  • [ 1621262-92-7 ]
YieldReaction ConditionsOperation in experiment
In tetrahydrofuran; methanol; for 0.75h;Reflux; The synthesis was done by adapting the previous reported method [21]. A solution of 0.2g (0.29×10-3mol) 5,10,15,20-meso-tetra(3-hydroxyphenyl) porphyrin in 60mL THF is brought to reflux under intense stirring in a round bottom three necked flask equipped with magnetic stirrer and refrigerator. Another solution comprised of 0.72g (3.02×10-3mol) CoCl2×6H2O dissolved in 40mL CH3OH is heated and then dropwise added to the porphyrin solution (final molar ratio porphyrin: metal salt=1:10). The reaction is monitored by registering the UV-vis spectra every 10min (Fig.2). The refluxing and stirring of the mixture are maintained for 45min. The solvent mixture is evaporated then the dry product is repeatedly washed with distilled water until the water is clear and all the excess cobalt salt is removed. The product is then dried and recrystallized from CHCl3.
  • 51
  • [ 22112-79-4 ]
  • C64H60N4NiO12 [ No CAS ]
  • 52
  • [ 22112-79-4 ]
  • C60H52N4NiO12 [ No CAS ]
  • 53
  • [ 5454-83-1 ]
  • [ 22112-79-4 ]
  • C68H70N4O12 [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% 5,10,15,20-Tetrakis(3’-hydroxy)phenylporphyrin 14 (400 mg, 0.59 mmol) was dissolved in anhydrous DMF (12 mL) underargon. K2CO3 (976 mg, 7.07 mmol) was added and the solution was stirred at rt for 0.5 h. Methyl5-bromovalerate (1.01 mL, 7.072 mmol) was added and the reaction was stirred for 24 h at roomtemperature. The solvents were removed in vacuo, the residue dissolved in CH2Cl2, washed withsaturated aqueous NaHCO3 (4×100 mL), brine (2×100 mL) and water (2×100 mL), dried over Na2SO4,and filtered. The solvents were removed in vacuo and the residue purified via columnchromatography on silica gel (CH2Cl2). The solvents were removed to yield an oil-like, purpleproduct. Yield: 512 mg (0.45 mmol, 77%)
  • 54
  • [ 5454-83-1 ]
  • [ 22112-79-4 ]
  • C68H68N4O12Zn [ No CAS ]
  • 55
  • bis(acetylacetonate)nickel(II) [ No CAS ]
  • [ 22112-79-4 ]
  • [tetrakis(3’-hydroxy)phenylporphyrinato]nickel(II) [ No CAS ]
  • 56
  • [ 22112-79-4 ]
  • [ 142-71-2 ]
  • [ 591751-85-8 ]
YieldReaction ConditionsOperation in experiment
With acetic acid; at 24.84℃;Kinetics; General procedure: The reactions of complexing between porphyrins and copper acetate were studied by means of spectrophotometry in the range of 293-318 K. The change in temperature during the experiment did not exceed±0.1 K.
  • 57
  • [ 22112-79-4 ]
  • 5-(3-(10,15,20-tris(3-hydroxyphenyl)porphyrin-5-yl)phenoxy)pentanoic acid [ No CAS ]
  • 58
  • [ 22112-79-4 ]
  • 5-(3-(10,15,20-tris(3-acetoxyphenyl)porphyrin-5-yl)phenoxy)pentanoic acid [ No CAS ]
  • 59
  • [ 14660-52-7 ]
  • [ 22112-79-4 ]
  • ethyl 5-(3-(10,15,20-tris(3-hydroxyphenyl)porphyrin-5-yl)phenoxy)pentanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
28% STEP 1: Synthesis of ethyl 5-(3-(10,15,20-tris(3-hydroxyphenyl)porphyrin-5- yl)phenoxy) pentanoate) (2). A mixture of meso-tetrakis(3-hydroxyphenyl)porphyrin 1 (1.25 g, 1.84 mmol) and K2CO3 (0.5 g) in DMF (30 mL) was stirred under nitrogen at room temperature for 30 min. Ethyl 5-bromopentanoate (1.15 g, 5.5 mmol, 3 eq.) was added. The mixture was stirred at room temperature overnight. The reaction mixture was diluted with DCM, washed with water, satd .NaHCO3 (aq), water and brine, dried over Na2SO4, and evaporated. The crude residue was purified with two successive column chromatographies to give 2 (0.42 g, 28%).1H- NMR (300 MHz, DMSO-d6): ^ 12.0 (s, 1H), 9.90 (s, 3H), 8.88 (s, 8H), 7.66-7.79 (m, 3H), 7.52- 7.65 (m, 9H), 7.36 -7.7.42 (m, 1H), 7.18-7.26 (m, 3H), 4.12-4.20 (m, 2H), 4.05 (q, 2H), 2.34- 2.40 (m,2H), 1.65-1.85 (m, 4H), 1.12(t, 3H).
  • 60
  • [ 22112-79-4 ]
  • [ 36839-56-2 ]
  • C76H90I4N4O16 [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With potassium carbonate; In N,N-dimethyl-formamide; at 65℃;Inert atmosphere; (1) Under the protection of nitrogen, the porphyrin raw material was 49.0 mg (0.05 mmol) of P6-OH (5,10,15,20-tetrakis(3-hydroxyphenyl)-21H,23H-porphyrin) (Fig. 2 Indicated), 414.0 mg (1 mmol) of diiodotetraethylene glycol (I-PEG-I) (shown in Figure 1) and 69 mg (0.5 mmol) of potassium carbonate (K2CO3) were dissolved in 5 mL of anhydrous DMF. The temperature was raised to 65 DEG C. The reaction was terminated by TLC, and the solvent was removed to obtain a crude product. The crude product was separated on a silica gel column to obtain the purple porphyrin intermediate P6-I. The structural formula was shown in FIG. 3 with a yield of 70%.
  • 61
  • [ 20485-41-0 ]
  • [ 22112-79-4 ]
  • C49H33N5O5S [ No CAS ]
  • 62
  • [ 20485-41-0 ]
  • [ 22112-79-4 ]
  • C64H42N8O8S4 [ No CAS ]
  • 63
  • [ 22112-79-4 ]
  • [ 51146-56-6 ]
  • C96H94N4O8 [ No CAS ]
  • 64
  • [ 22112-79-4 ]
  • [ 39637-74-6 ]
  • C84H78N4O16 [ No CAS ]
  • 65
  • [ 32231-50-8 ]
  • [ 22112-79-4 ]
  • C64H62N4O8 [ No CAS ]
  • 66
  • [ 22112-79-4 ]
  • palladium dichloride [ No CAS ]
  • Pd(II)-mesotetra(m-hydroxyphenyl)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
In N,N-dimethyl-formamide; for 2h;Reflux; PdTPP, PdTpAP, PdTmCPP, and PdTmCPP [10]: 5 mmol of porphyrin (TPP/TpAP/TmHPP/TmCPP), 7.5 mmol of PdCl2 in 20 mL DMF were refluxed for 2 h, cooled to rt,and filtered. The filtrate was diluted with 40 mL EtOAc, washed using 2 20 mL of waterand 2 15 mL of brine. EtOAc was evaporated in vacuo and the resultant residue of thePd-porphyrin complexes subjected to purification using CC with eluent,MeOH:CH2Cl2 (5:95).
  • 67
  • [ 22112-79-4 ]
  • [ 6046-93-1 ]
  • [ 591751-85-8 ]
YieldReaction ConditionsOperation in experiment
74% for 0.5h;Milling; General procedure: A mixture of the porphyrin (50 mg), the metal salt (5 equivalent) and two stainlesssteel spheres (7 mm of diameter) were placed in the stainless-steel jar and submitted tomechanical action in a ball milling system (Retsch 400 MM) at 25 Hz during 30-90 min.The reaction was followed by UV-Vis at each 30 min. Once complete, the reaction productwas scraped to empty the jar. Hydrophobic porphyrins were purified through liquid-liquid extraction using ethyl acetate and water, the organic phase was dried with Na2SO4anhydride and the solvent removed through evaporation. Water-soluble porphyrinswere purified through exclusion chromatography (Sephadex G-10) using water as eluent,followed by water evaporation.
  • 68
  • [ 22112-79-4 ]
  • [ 55216-11-0 ]
  • C44H30N4O4*2C63H112O35 [ No CAS ]
YieldReaction ConditionsOperation in experiment
for 1.5h;Milling; General procedure: TPPOCOOHC2 (1.90 mg, 2.76 μmol) and pMβCD (3.92 mg, 2.74μmol) were placed in a mortar and were pulverized vigorously with apestle for ~1.5 h. The brown solid mixture obtained was suspended in4% DMSO in D2O (v/v) (0.6 mL) solvent mixture to produce a red solution.The solution was then sonicated for 1 min and vortexed foradditional 2 min. The concentration of the complex in the solution wasdetermined to be 1.75 mM by measuring the ratio of integrals of thepMβCD H1 signal in free and complexed form, in the 1H NMR spectra.
Same Skeleton Products
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